Process for the manufacture of viscose fibres with novel dyeing properties

ABSTRACT

A PROCESS IF PROVIDED FOR THE MANUFACTURE OF VISCOSE FIBRES WITH IMPROVED DYEING PROPERTIES. IN THIS PROCESS A POLYAMINE-AMIDE FROM (A) A HIGHER UNSATURATED FATTY ACID OR ITS DIMER OR POLYMER AND (B) A POLYALKYLENE-POLYAMINE AND A FURTHER REACTION PRODUCT OF (C) A POLYEPOXIDE COMPOUND AND (D) A STOICHIOMETRIC EXCESS OF A POLYALKYLENEPOLYAMINE ARE INCORPORATED INTO THE VISCOSE SPINNING SOLUTION IN A FINELY DIVIDED FORM FROM WHICH SPINNING SOLUTION THE VISCOSE BEING THEREAFTER PRECIPITATED AND SHAPED. THE FIBRES OBTAINED SHOW A GOOD RECEPTIVITY FOR DYESTUFFS SUITABLE FOR DYEING CELLULOSE MATERIALS AND ALSO FOR ACID WOOL DYESTUFFS AND DISPERSION DYESTUFFS.

United States Patent 3,793,419 PROCESS FOR THE MANUFACTURE OF VISCOSEFIBRES WITH NOVEL DYEING PROPERTIES Felix Steinlin, Dornach, Soleure,and Horst Nobs, Magden, Aargou, Switzerland, assignors to Ciba-Geigy AG,Basel, Switzerland No Drawing. Continuation of abandoned applicationSer. No. 858,138, Sept. 15, 1969. This application Jan. 31, 1972, Ser.No. 222,319 Claims priority, application Switzerland, Oct. 1, 1968,14,660/ 68 Int. Cl. D011 3/12 US. Cl. 264-78 8' Claims ABSTRACT OF THEDISCLOSURE A process is provided for the manufacture of viscose fibreswith improved dyeing properties. -In this process a polyamine-amide from(a) a higher unsaturated fatty acid or its dimer or polymer and (b) apolyalkylene-polyamine and a further reaction product of (c) apolyepoxide compound and (d) a stoichiometric excess of apolyalkylenepolyamine are incorporated into the viscose spinningsolution in a finely divided form from which spinning solution theviscose being thereafter precipitated and shaped.

The fibres obtained show a good receptivity for dyestuffs suitable fordyeing cellulose materials and also for acid wool dyestuffs anddispersion dyestuffs.

This is a continuation of application Ser. No. 858,138 filed on Sept.15, 1969' and now abandoned.

The present invention relates to a process for the manufacture ofviscose fibres having novel dyeing properties. According to the presentinvention there is provided a process for the manufacture of viscosefibres which comprises adding to the viscose spinning solution beforeprecipitation of a polyamide-amide derived from (a) an unsaturated fattyacid with at least 12 carbon atoms or a dimer or polymer thereof and,(b) a polyalkylene-polyamine, and a further reaction product of (c) apolyepoxide compound and (d) a stoichiometric excess of apolyalkylene-polyamine, the additives being in finely divided form andadded in an amount totalling 1 to 20%, preferably 1 to 12% by weightrelative to the cellulose content in the spinning solution.

The nitrogen-containing additives employed in the process of thisinvention are known compounds, which can be incorporated into theviscose spinning solution in an aqueous medium, appropriately, with theaid of emulsifiers; they have good compatibility with the viscose.

To manufacture the amides containing amino groups;

aliphatic, unsaturated monocarboxylic acids with at least are alsosuitable. The unsaturated fatty acids can also be used mixed with theirdimerized, or polymerized deriva tvies, or the dimers or polymers may beused instead of the monomers. The polymerization of the acids probablytakes place by a Diels-Alder mechanism, in that conjugated and,therefore, reactive carbon-carbon double bonds are produced in theunsaturated fatty acids by a partial or complete isomerization, thesedouble bonds then completing the reaction to give a mixture of dimericand higher polymeric fatty acids. Of course such a reaction can onlytake place if a starting material contains at least two conjugatedcarbon-carbon double bonds. With oleic acid, for example, it can onlyreact if another compound having at least two conjugated double bonds ispresent.

Aliphatic polyamines with at least two primary or secondary aminegroups, such as ethylenediamine, diethylenetiamine andtriethylenetetramine, serve as component In addition to adding thepol'yamine-amide derived from components (a) and (b), it is required toadd it to the viscose spinning composition with a further reactionproduct of a polyepoxide (c) and a stoichiometric excess of apolyalkylene-polyamine (d).

Suitable polyepoxides which may be used include the polyglycidyl etherssuch as those accessible by etherification of a dihydric alcohol ordiphenol with epichlorohydrin in the presence of alkali. The epoxideswhich are obtained by reaction of bis(p-hydroxyphenyl)-dimethylmethaneBisphenol A) with epichlorohydrin should be particularly mentioned.Reaction of these products with the polyamines (d) then yields thesecond additive.

The polyamines (d) may be the same or similar to the amines which havebeen mentioned for component (b). The adduct of (c) and (d) contains nofurther free epoxide groups since a stoichiometric excess of amine isalways used.

The amounts of the components (a) to (d) which are reacted can varywithin wide limits. Thus the amides containing amine groups may, forexample, contain 40 to 80% by weight of fatty acid or dimerized orpolymerized fatty acid and '60 to 20% by weight of polyamine whilst theepoxide-amine compound is suitably derived from 25 to 40% by weight ofan epoxide compound and 75 to 60% by weight of polyamine.

The additives (a) are added 90 to 10% by weight being a polyamine-amidederived from (a) and (b) and 10 to 90% by weight being a reactionproduct of (c) and (d).

In addition to the essential additions described above, the reactionproducts may contain furthed additives, such as solvents and additionalreagents such as epoxides and phenols.

The product of (a) and (b), mixed with a. product of (c) and (d), aresuitably introduced in an aqueous medium into the viscose spinningsolution. If the products are not water-soluble or only show limitedsolubility in water, an aqueous medium can be used which containsemulsifiers and/or organic solvents. The emulsifiers used can be anionicor cationic, but are preferably non-ionic. Suitable non-ionicemulsifiers include the addition products of 4 to 12 mols of ethyleneoxide to long chain amines or alcohols with 12 to 24 carbon atoms or toalkylphenols with 10 to 18 carbon atoms. The emulsifiers are generallyemployed in amounts of between 1 and 20%, preferably between 1 and 5% byweight relative to the cellulose. The compounds and preparationsintended for the manufacture of the viscose with novel dyeing propertiescan now be stirred directly in finely dividedform into the spinningsolution. The filtratability of the viscose is generally not adverselyaffected by the presence of the additives, so that during the spinningprocess blocking of sieven mounted in front of the spinning nozzlearising from the presence of such additives, does not occur and ahomogeneous filament material can be manufactured without fluctuationsin gauge. The shaping of the viscose may be carried out in known maner,e.g. through spinnerets into a precipitation bath (e.g. a Muller bath)with optional post-treatment in further baths.

I .,ing nitrogen-containing fibres or polyester material, may

also be used.

Thus many useful dyestuffs can be used for dyeing cellulose material asa result of the process of this invention. These dyestuffsgenerallyyield uniform and nonstripy dyeings with good fastness properties on thecellulosic material manufactured according to, the invention.

Amongst the many known acid wool dyestuffs which can be used here, theremay especially be mentioned the metal-containing dyestuffs such as1:2-chromium or cobalt complex dyestuffs, the dyestulf molecule of whichcan contain free acid groups conferring solubility in water, or 1:1metal complex dyestuffs. Of the dispersion'dyestuffs, azo andanthraquinone dyestuffs should particularly be mentioned.

The cellulose material manufactured according to this invention behavesparticularly well in a mixture with, for example, untreated cellulosicfibres. 'Here it is possible to achieve, with a dyestuff mixture of adirect dyestuff and wool dyestuff, applied from a single dyebath, dyeingeffects and color patterns which are determined by the fibredistribution (for example strips of any desired width and any desiredspacing) in the mixed fabric. The direct dyestuff dyes the entire fabricwhilst the wool dyestutf only dyes the fibres in the fabric which hasbeen manufactured according to the invention (differential dying).

Tone-in-tone dyeings of fibre mixtures of the fibre material accordingto the invention and wool/polyamides or polyester fibre material can beobtained using wool or dispersion dyestutf.

The dyeing of the material may be carried out in the usual manner forthese dyestuffs, for example, according to the padding process or theexhaustion process at an elevated temperature. I

The essential advantage of the cellulose material manufactured accordingto this invention resides in the fact it remains cellulose like and,nevertheless, possesses the novel dyeing properties described. It thusdiffers from the so-called animalized cellulosic fibres which areobtained from viscose spinning composition into which large amounts ofnitrogen-containing substances are incorporated. These animalizedcellulosic fibres have partially lost the dyeing properties of celluloseand in this respect behave more like wool. a g

The following examples further illustrate the present invention. Unlessotherwise stated, the parts quoted in the example are parts by weight.

EXAMPLE I 5 g. of the preparation A described below are emulsified with5 g. of an addition product of 8 mols of ethylene oxide to 1 mol ofp-tert.octylphenol, filtered and stirred into 983 g. of viscos g. ofcellulose). The viscose is spun in the usual manner with the aid of aprecipitation bath containing sulphuric acid to give long fibres. Thefibres are subsequently washed in after-treatment baths (for examplewater desulphurized (for example with dilute aqueous solutions of sodiumsulphide. and sodium hydroxide) washed and brightened.

Preparation A consists of 28.6 parts of a Component I and 71.4 partsof'a Component II. Component I is manufactured as follows: A reactionmixture of 48.2 parts of diethylenetriamine, 34.6 parts of bisphenol Aand 17.2 parts of a bisphenol A-epichlorohydrin resin with 182 to 191epoxide equivalents per kg. of resin is reacted for about 5 hours at 200C., with the'volatile constituents being distilled ofi towards the endof the reaction by -applying a water pump vacuum.

Component II is manufactured as follows: A mixture of 40 parts oftalloil fatty acid and 13.8 parts of dimerised fatty acids is heated to C.whilst stirring and is mixed with 34 parts of triethylenetetramine atthis temperature. The temperature is then raised to 200 C. and is keptfor 3 hours at this value, with a water pump vacuum being applied in thelast hour.

The resulting polyamine-amide is then further mixed with 17.2 parts ofxylene.

The cellulose material manufactured with this preparation can be welldyed with acid wool dyestutf and dispersion dyestuffs according to themethods known for dyeing .with these dyestuffs. Suitable dyestuffs are,amongst others:

1:2-ehromlum complex (1) HO OH H0 Reddish brown:

, l c=N I Hg N0 I 8 0d! 1 g v v 1:2-cobalt complex (2 .1321: HO Yellow.

CH; N=NC I C= H]- OQNHCHI 1:2-chromium complex 3 HO Oran B; Ho 8 N=NC\ II OzNHz 1:2-chrom1um complex TABLEContlnued 1 Z-chromium complex ZL'O TN=NC S 02C H 1:2-eobalt complex OZNH(CH:)3O CH1 1 :2cobalt complex OH HO0 zN l (7) O NH:

YN Omzoocmcr 1:1-chromlum complex (9).....'...' O NH1 OCH;

i) NH-S 00cm a NE Red.

Claret.

Violet:

Blue:

Yellow.

Pink.

Blue:

7.5 g. of the Preparation B described below are filtered in the form ofa strength aqueous solution and stirred into 983 g. of viscose (75 g. ofcellulose).

The viscose is spun as described in Example 1 and the fiber material isappropriately after-treated. Preparation B is manufactured as follows:

A solution of 49.4 g. of 'a condensation product of polymerized linoleicacid and diethylenetriamine having an amine equivalent of 247, and 49.4g. of methanol, are

added over the course of 24 minutes, with good stirring, into asolution, warmed to 51 C., of 38.4 g. of an epoxide formed from4,4'-dihydroxydiphenyl-Z,2'-propane and epichlorhydrin, having anepoxide equivalent of 191, and 38.4 g. of methanol, the reactiontemperature being 51 to 53 C. 3 g. of glacial acetic acid are addedafter 8 minutes and again after 18 minutes from the start of thedropwise addition, and after 24 minutes a further 2 g. of glacial aceticacid are added. The reaction is continued for a further 2 hours andminutes at 55 to C. The reaction product is then soluble in water toform an opalescent solution. Thereafter 4 g. of glacial acetic acid and273.4 g. of water are added whilst stirring. A yellowish viscous cloudy20% solution having a pH-value of 5.2 is obtained.

A mixed cellulosic fabric of viscose fibres and fibres manufacturedaccording to the invention with Preparation B, the latter having beenwoven in as stripes, is dyed by 7 the exhaustion process, in a knownmanner, with the following dyestufls:

A fast blue dyeing with violet stripes is obtained.

We claim:

1. A process for the manufacture of viscose fibers with novel dyeingproperties, which comprises adding to the viscose spinning solutionbefore precipitation from 1 to 20% by weight, based on the weight ofcellulose content in said spinning solution, of a mixture comprising:

(A) from 90 to by weight of a polyamine-amide obtained by reacting (a)from 40 to 80% by weight of an unsaturated fatty acid with at least 12carbon atoms or a dimer or polymer thereof and, (b) from to 60% byweight of a polyalkylene-polyamine; and

(B) from 10 to 90% by weight of a polyepoxide-polyamine product obtainedby reacting (c) from to 40% by weight of a polyepoxide and (d) astoichiometric excess of a polyal-kylene-polyamine, saidpolyalkylene-polyamine being present in an amount of from 75 to 60% byweight.

2. A process according to claim 1 wherein (a) is an --unsaturated fattyacid With"'l 2 to"l8 carbon atoms'or a' dimeror polymer thereof. 1 1.

3. A process according to claim 1 wherein (c) i s a;

reaction product of Bi'sphenol A andepichlorohydrin.

4. A" process "according to claimil wherein (b) and (d) isethylenediarnine, diethylenetr'iarnine or triethylenetetramine. ,1 f v5. A process according to claim 1 wherein the additives derived from (a)and"'(b) and from (c) and (d) are added to the spinning solution asanaqueous or organic solution or a dispersion. 6; t 1

6. A process according to claim 5 wherein the additives are added to thespinning-"solution inthepiesence of a non-ionic emulsifier. 1

7. A process according to claiml whereinthej additives are added to 10%by weight being a polyaniine-amide derived from (a) and (b) and .10.to90%;;byweight being a reaction product of (c) and (d), W

8. A process according to clairn 1 hereln the additives are added in anamount totalling 1 to 512% by wei ght based on the celluloseconte'nt inthe spinning solution. Reference Cited r UNITED STATES RATENTS 2,767,08910/1956 Renfrew 61111. Gil -2i 2,852,334 9/1958 Hollihauet 211,1" 0644442,971,816 2/1961 Hollihan et a1. 3 264-193 3,016,305 1/1962 Vosfers106-165 3,046,085 7/1962 Burroughs et al.- 264-194 3,066,032. l1/.1 962.Fukushima et al 106165 3,106,444' -10/196'3 Mueller; 264-194 3,278,56010/1966 Garbner .-s 116.2

FOREIGN PATENTS H 37-17771 10/1962 Japan 264-188 .TAY H. WOO, PrimaryExaminer "Us, c1. X.R.

